Hydrochloric Acid → Ethyl 2-(1-hydroxy-4-methyl-6-(5-nitro-1,3,4-thiadiazol-2-yloxy)-1,3-dihydrobenzo[c][1,2]oxaborol-3-yl)propanoate

HRID 1798310Notes

Reaction equation

HRID 1798310 reaction equation
[OH:1][B:2]1[C:6]2[CH:7]=[C:8]([OH:12])[CH:9]=[C:10]([CH3:11])[C:5]=2[CH:4]([CH:13]([CH3:19])[C:14]([O:16][CH2:17][CH3:18])=[O:15])[O:3]1.Br[C:21]1[S:22][C:23]([N+:26]([O-:28])=[O:27])=[N:24][N:25]=1.Cl>CC#N>[OH:1][B:2]1[C:6]2[CH:7]=[C:8]([O:12][C:21]3[S:22][C:23]([N+:26]([O-:28])=[O:27])=[N:24][N:25]=3)[CH:9]=[C:10]([CH3:11])[C:5]=2[CH:4]([CH:13]([CH3:19])[C:14]([O:16][CH2:17][CH3:18])=[O:15])[O:3]1

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 122078702-Bromo-5-nitro-1,3,4-thiadiazoleHCID 58292822Ethyl 2-(1,6-dihydroxy-4-methyl-1,3-dihydrobenzo[c][1,2]oxaborol-3-yl)propanoate

Product 1

HCID 58292599Ethyl 2-(1-hydroxy-4-methyl-6-(5-nitro-1,3,4-thiadiazol-2-yloxy)-1,3-dihydrobenzo[c][1,2]oxaborol-3-yl)propanoate

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

Into a 50-mL round-bottom flask were placed a solution of ethyl 2-(1,6-dihydroxy-4-methyl-1,3-dihydrobenzo[c][1,2]oxaborol-3-yl)propanoate (800 mg, 2.73 mmol, 1.00 equiv, 90%) in CH3CN (30 mL), KHCO3 (1.5 g, 15.00 mmol, 5.00 equiv) and 2-bromo-5-nitro-1,3,4-thiadiazole (890 mg, 3.80 mmol, 1.40 equiv, 90%). The resulting mixture was stirred overnight at room temperature. The pH value of the solution was adjusted to 4 with HCl (2 mol/L), then extracted with 4×50 mL of ethyl acetate. The organic layers were combined, washed with 2×50 mL of brine, dried over anhydrous sodium sulfate and concentrated under vacuum. The residue was applied onto a silica gel column and eluted with ethyl acetate/petroleum ether (1:2). This resulted in 0.4 g (22%) of ethyl 2-(1-hydroxy-4-methyl-6-(5-nitro-1,3,4-thiadiazol-2-yloxy)-1,3-dihydrobenzo[c][1,2]oxaborol-3-yl)propanoate as a brown oil.

Workup

  1. customInto a 50-mL round-bottom flask were placed
  2. extractionextracted with 4×50 mL of ethyl acetate
  3. washwashed with 2×50 mL of brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated under vacuum
  6. washeluted with ethyl acetate/petroleum ether (1:2)
  7. customThis resulted in 0.4 g (22%) of ethyl 2-(1-hydroxy-4-methyl-6-(5-nitro-1,3,4-thiadiazol-2-yloxy)-1,3-dihydrobenzo[c][1,2]oxaborol-3-yl)propanoate as a brown oil

Sources & evidence

ORD record
ord-f643f2800ce64bafa1a7f7596c6bd93b
Source dataset
uspto-grants-2013_01
Patent number
US08343944B2

Reaction notes

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